Process for breaking petroleum emulsions



Patented yROCESS FOBEBBE a rn'rnnm M'ULSION S elvln De Groote, University City, and B l Groves,

Kaiser, Webster Ma, assignom Fetrolite Corporation, Ltd, Wilmington, Del., a corporation oi Delaware.

No Bras.

This invention relates primarily to the resolutlon of petroleum emulsions.

One object of our invention is to providev a novel process for resolving petroleum emulsions of the water-in-oil type, thatare commonly referred to as cut oil," roily oil, "emulsified oil," etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion.

Another object is to provide an economical and rapid process for separating emulsions which have been prepared under controlled conditions from mineral oil, such. as crude petroleum and relatively soft waters or weal: hrines. Controlled emulsincation and subsequent demulsiflcation under the conditions just mentioned is oi significant value in removing impurities, particularly inorganic salts, from pipeline oil.

The chemical compound or composition of matter herein described that is employed as the demulslfier of our process, is a new material, representing a sub-genus of a broad class of sulfation derivatives which may he in the form of an ester, a salt, or arr-acid, but preferably, in one of thetwo last mentioned iorms. if a high molal sulfonic acid be indicated by the conventional formula: f

RSOsH then a hydroxylated ester which may actually have more than one hydroml group in the radical which replaces the sulfonic d hydrogen atom, may be indicated by the following formula:

RBOaTOH If such ester, for instance, the ester derived from ethylene glycoL'is treated with sulfuric acid, one then can obtain a sulfate of the sulfonlc acid ester, as indicated in the following manner:

I nsoaognigtjjfi-jignsor I'he neutralization product derived therefrom by the use of onium hydroxide, for example, may be indicated by the follo formula:

' to sulfation, be water-insoluble; and v Application January 25, 1941, Serial No. 375,980

(c) That the sulfonic acid be derived from certain alicyclic compounds hereinafter specified.

face tension in comparison with distilled water.

Usually, the acids themselves show the same surface-active property as the salts.

Although the types of compounds employed as the demulsifler in the present process are new chemical products, certain oi. the raw materials used in the manufacture of said. chemical products, to wit, alicyclic sulfonic acids derived from the group consisting of dipentene, the diamylenes, turpentine, alpha and beta pinches, pine oil, abietic acid, methyl abletate, tallol, and dim dromethyl abietate, are well known compositions of matter. However, as they maybe derived in a variety of ways and may show a clifierence in degree, reference is herein made to suitable means for obtaining alicyclic sulfonic acids derived from the group consisting of dipentene, the

Sil

diamylenes, turpentine, alpha and beta pinenes, pine oil, abletlc acid, methyl abietate, tallol, and dihydromethyl abietate, particularly adapted as raw materials in the manufacture of compounds of the kind herein contemplated.

It is obvious that the procedure herein described is applicable to the manufacture of var ious surface-active sulfonic acids; such as fatty sulfonic' acids, fatty aromatic ,sulfonic acids, alkylaryl sulfonlc acids, and the like. Such broad aspect is contemplated in our co-pending application, Serial No. 375,9?4, filed January 25, 1941, in which there is detailed description of a large variety of acceptable types of sulfonic acids which may be employed reacants to produce compounds analogous to the particular specie or sub-genus herein contemplated.

The present invention relates, to a broad sub- .genus of the class just described. It is concerned only with sulionic acids derived from certain alicyclic compounds such as resin or abietlc acid, and also the peculiar natural mixture of abietic acid and fatty acids which occur as tallol. Tallol is the liquid resin commonly known as "tall oil," or "talloP (EllirLChemistry of Synthetic Resins,

. .1935, Vol. 1, pages 754-755) Crude tallol varies somewhat in composition,

but an approximate average of its constituents is indicated as follows:

The resin acids crystallize from tallol at ordinary temperatures, but will readily go into solution when the mixture is warmed. Re-crystallization is often slow, if all crystal nuclei are melted prior to cooling, so the material may readily be handled in a homogeneous state. The fatty acids are all of unsaturated nature.

As to procedures concerned with the manufacture of sulfonic acid salts from tallol, which can readily be altered so as to yield tallol suifonic acids, attention is directed to'British Patent No. 369,985 (1931) to Imperial Chemical Industries, Ltd. Attention is also directed to British Patent No. 340,279 (1930) to Johnson, on behalf of I. G. Farbenindustrie Aktiengesellschaft. A convenient method for the manufacture of sulfonic acids from tallol is to convert the same into esters, with or. without hydrogenation, as suggested, in the said aforementioned British Patent No. 369,985, or in the manner described in U. 8. Patent No. 1,877,179, dated September 13, 1932, to Humphrey. Such esters, if derived from a polyhydric alcohol, for instance, ethylene glycol, glycerol or the like, can be reacted with a low-molal alpha-chloro aliphatic acid, such as chloroa'cetic acid, so as to give the'corresponding ester. Such ester can then be treated with sodium sulfite in the conventional manner to give the corresponding sulfonic acid with the elimination of sodium chloride. The sulfonic' acid salt, so obtained, can be treated 'in the manner.

previously indicated, in order to obtain the free sulfonic acid. A similar procedure has been indicated in the aforementioned United States patent.

A preferred procedure, however, is to chlorinate tallol in the conventional manner and then react the chlorinated tallol with an aromatic material,

such as benzene, naphthalene, phenol or the like,

in the presence of a condensing agent, such as aluminum chloride, or similar reagents, in a manner similar to that emploved in connection with fatty acids, as described in Industrial 8; Engineering Chemistry, July 1939, pp. 856-858, and Industrial a Engineering Chemistry, August 1940, pp. 1138-37. Another preferred procedure is to manufacture sulfo-aromatic derivatives of tallol employing the method described in the aforementioned n. s. Patent No, Lamaze: At-

tention is also directed to U. S. Patent No; 1,289,079, dated December 31, 1918, to Boehrinaer.

However, instead of using tallol, or resin abietic acid or the like. one may employ materials such as dipentene, the diamylenes, turpentine, alpha and beta pinenes, pine oil, methyl abietate. tallol, and dihydromethyl abietate, etc.

As specific examples of desirable sulfonic acids,

reference is made to alpha-pinene hydroxy sulfonic acids, beta-pinene hydroxy sulfonic acids.

hydroxy sulfonic derivatives of abietic acid and is found in U. S. Patent No. 2,220,878, dated November 5, 1940, to Cromwell andMerley. Our

preference is to employ the procedure indicated in Example 1' of the aforementioned Cromwell 'terial of the following type:

et al. patent in water-soluble sulfonic acid of dipentene.

,The procedure of manufacturing hydroxylated esters of sulfonic acids is well known, although direct reaction between a sulfonic acid and a polyhydric'alcohol such as ethylene glycol, is not applicable, for the reason that one obtains little or no yield of the hydroxylated-ester. One procedure contemplates the conversion of sulfonic.

is to use the procedure described in U, S. Patent No. 2,208,581, dated July 23, 1940, to Hoefrelmann. Briefly stated, the procedure employed isto obtain a free'sulfonic acid in an anhydrous state, and treat with a compound containing an ethylene oxide radical. As typical examples of applicable compounds may be mentioned glycerine epichlorhydrin, glycide alcohol, ethylene oxide, propylene oxide, butene-2-oxide, butenel-oxide, isobutylene omde, butadiene oxide. butadiene dioxide, chloroprene oxide, isoprene oxide, decene oxide, styrene oxide, cyclohexylene oxide, cyclopentene oxide, etc.

Note, however, that there are certain differences between the procedure employed for the manufacture of, the intermediate raw material and the procedure as employed in said aforementioned Hoeifelmann patent. The. Hoefielmann method contemplates treatment of sulfonic acids which are not necessarily surface-active, for instance, benzene-sulfonic acid, with an olefine oxide, so as to produce materials, which, for the main part, are water-soluble and surface-active. It happens that invariably the esters of the high molal sulfonic acids are insoluble iii-the absence of a recurring ether linkage. In order to obtain compounds of the kind herein contemplated, one must stop treatment with the olefine oxide, i. e.. owaikylation, before water solubility is obtained; and furthermore, it is desirable to stop water solubility at the earliest stage; In other words, the ole oxide employed, whether ethylene oxide, propyleneoxide, butylene oxide, glycidoi, methyl glycidol, or. the like, is a comparatively expensive reagent; and one is only concerned with obtaining a reactive hydroxyl radical for a subsequent sulfation step. There is no objection to the presence of a recurring ether linkage, provided that the ester is still water-insoluble. This may be illustrated in the following manner, using ethylene oxide as the reactant:

One is interestedprimarily in obtaining a maasoaozmorr But materials iilustrated by any of the three sub- 1 sequent types:

RSOsCzHtOCQHeOH RSOaCzHeOCerhOCaHaOI-I Rsouonnomr are just as satisfactory, provided that the ester, prior to sulfation, is water-insoluble. In some instances the presence of the recurring ether linkage may give some added desirable characteristic. Ordinarily speaking, one is concerned only with minimum reactant cost; and thus, the use of an excess amount of the olefine oxide is not justified. One is not attempting to obtain water solubility by means of the expensive oxyalkylation step. As has been emphasized, the ester obtained must be water-insoluble, regardless of how much or how little alkylene oxide is employed. Generally speaking, 40 moles of alkylene oxide per mole of sulfonic acid may be considered as an upper limit, but obviously solubility is infiuenced by the alkylene oxide employed. Butylene oxide naturally will not cause a sulfonic acid to be converted into a water-soluble. ester as readily as ethylene oxide.

Thus, having obtained hydroxylated water-insoluble esters-and they may be polyhydroxylated and may or may not contain the recurring ether linkage-the next step is to submit them to a conventional sulfation process. The sulfation of such materials is the conventional procedure employed for the sulfation of fatty acids or fats containing the hydroxyl radical or ethylene linkage, such as oleic acid, olein, ricinoleic acid, triricinolein, monostearin, and the like. A similar procedure is employed in the sulfation of amides derived from fatty acids and hydroxylated amines, such as the stearic acid amide of monoethanolamine. A similar procedure is employed in connection with the sulfation of high molal alcohols and other similar materials.

Briefly stated, the procedure consists in treating the material with the amount of sufating agent at least molecularly equal to the material to be sulfated; and usually the sulfating agent is employed in considerable excess, for instance, from 50% excess to 200% excess, based on molal proportions. Sulfating agents include sulfuric acid of commerce, monohydrate, oleum of various strengths, chlorosulfonic acid, sulfamic acid, etc. Sulfonation is generally conducted at a relatively low temperature, from approximately, zero degrees Centigrade to a temperature of 3540 C. or thereabouts. Sulfation can be conducted in the presence of a solvent, such as liquid sulfur dioxide, chlorinated hydrocarbons, dioxane, ethyl ether, etc. Sometimes it is desirable to add materials which tend to take up any water which may be formed, such as acid anhydrides, including acetic anhydride. When sulfation is complete, which is usually indicated by absolutely clear solubility of the sulfated product, it is generally Washed immediately so as to remove the excess sulfating agent. Washing is generally conducted with cold water, chilled brine. or ice. The sulfated material is permitted to separate and the dilute draw-oil acid withdrawn. The sulfated mass may be employed as such, or may be neutralized in any convenient manner with any one of the conventional basic materials frequently employed, such as caustic soda, caustic potash. ammonia, various hydroxylated amines, including monoethanolamine, diethanolamine, triethanolamine; and non-hydroxylated amines. including amylamine, benzylamine, cyclohexylamine, and the like. Such materials may be neutralized with polyvalent compounds, such as calcium oxide, magnesium oxide, polyamines, including ethylene diamine, diethylene triamine, triethylene tetramine, etc.

' Example 1 Tallol is converted into the hydroxy ethyl ester in the manner described in Example 4 of aforementioned British Patent No. 340,272. The bydroxy ethyl ester is then esterified in equal molal proportions with chloracetic acid. The product, so obtained, is treated in the conventional man- 'ner with one mole of sodium sulfite with the elimination of sodium chloride. The sodium sulfonate, so obtained, is dissolved in alcohol and the free sulfonlc acid liberated in the manner previously suggested. The sulfonic acid, so obtained, is anhydrous, or can be converted into the anhydrous state by any suitable procedure. It may be heated to approximately to C. and dried carbon dioxide gas passed through until the material is anhydrous. It may be dried in a vacuum drier, so as to yield an anhydrous material. It may be distilled in the presence of an insoluble solvent, such as xylene, so that the xylene is permitted to carry oil water during the distillation. Vapors, so obtained, are condensed and the water separated from the xylene. The xylene can be returned for re-circulation, so as to carry oii more water.

Having obtained a non-hydrous material of the kind above described, it is diluted with several times its weight of anhydrous ethyl alcohol and refluxed until the carboxyl hydrogen atom has been replaced by an ethyl radical. One pound mole of the anhydrous ethylester sulfonic acid, so obtained, is treated with one to three moles of ethylene oxide in the manner described in the aforementioned Hoefielmann Patent No. 2,208,- 581, so as to yield a water-insoluble ester. Such ester is sulfated in the conventional manner employed for such type material with approximately 65% to 100% by weight of monohydrate. The sulfation is most conveniently conducted in apparatus designed to mix even solid materials with the sulfating agent. A sulfation temperature of approximately 35-45" C. is employed. The acid is added as rapidly as possible, and as a rule, sulfation can be completed within 24 hours. When sulfation is complete, the acid mass should give an absolutely clear, limpid, solution in water. Failure to obtain such clearly soluble sulfated mass is due to either over-sulfation or undersulfation. Over-sulfation means that the period of sulfatlon is too long and decomposition of the sulfated material took place progressively with sulfation. In such case, it is probable that the period of sulfation should be decreased somewhat. Under-sulfation can be corrected by increasing the volume of sulfating agent or increasing its activity, for instance, using a mixture of oleum and monohydrate, or else perhaps, extending the period of sulfation slightly. As is understood by those skilled in the art, such sulfation procedure depends upon the particular sulfation employed; and there is no diiiiculty in varying these factors so as to obtain absolutely water-soluble properties. When sulfation is complete, the mass is washed with cold water, or preferably, with a mixture of chipped ice and water. The amount of water added is preferably equal to the amount of sulfating agent added. The mixture is stirred and allowed to stand the minimum length of time necessary to give a complete separation. Sometirnes separation is hastened by the use of a chilled brine instead of water, or by the addition of a solvent, particularly if such solvent is not objectionable in the final product. Such solvent may be a material of the kind exemplified by xylene, kerosene, propyl ether, and the like. After separation is complete, the waste acid is withdrawn and the acid mass neutralized in Tallol is converted into the sodium salt-and reacted with sodium benzyl chloride sulfonate in the manner illustrated in Example 6 of the aforementioned U. 8. Patent No.l,9l6,776. The sulfonate, so obtained, is treated in the same manner as Example 1 of the present instance.

Example 3 Tallol is reacted with sodium hydroxyethane sulfonate in the manner described in Example i of the aforementioned U. 8. Patent No. 1,881,172, so as to yield the corresponding derivative. The material, so obtained, is converted in the same manner as in Example l of the present instance.

Example 4 Tallol is sulfonated in the manner described in mample a of the aforementioned U. S. Patent No. 1,926,442. The sulfonic acid, so obtained, is converted in the manner described in Example 1 of the present instance.

Example 5 Tallol is reacted with benzene and chlorosulfonic acid in the manner described in Example t of the aforementioned U. S. Patent No. 1,980,414. The acid mass, so obtained, is subjected to hydrolysis, so as to decompose any sulfates formed. The waste acid is then removed and the mass dried. Such dried mass is then diluted with several times its volume of ethyl alcohol and refluxed until any carboxyl radicals remaining are esterified, and thus converted into the ethyl ester. The excess of alcohol is removed and the sulfonic acid treated with ethylene oxide in subsequent steps in the manner exemplified by Example 1 of the present instance.

Example 6 Dipentene is converted into the water-soluble sulfonic acid following the specific directions of the aforementioned Cromwell and Merley Patent No. 2,220,678. The sulfonic acid so obtained is rendered anhydrous and converted into a water-insoluble ester by reaction with ethylene oxide and then sulfated in the manner indicated in Example 1, preceding.

Example 7 A mixture of diamylenes having a tertiary carbon atom at the double bond in their structure is sulfonated in the manner described in Example 2 of the aforementioned Cromwell and Marley patent. The sulfonic acid so obtained is rendered fated in the manner indicated in Example Lpreceding.

Example 9 A mixture of alpha and beta pinenes is sulfonated in the manner described in Example 4 of the aforementioned Cromwell and Merley patent. The. sulfonic acid so obtained is rendered anhydrous and converted into a water-insoluble anhydrous and converted into a water-insoluble ester by reaction with ethylene oxide and then sulfated in the manner indicated in Example 1, preceding.

Example 8 1 by reaction with ethylene oxide and then sulester by reaction with ethylene oxide and then enlisted in the manner indicated in Example 1, preceding. 4

Example 10 A crude distilled pine oil is sulfonated in the manner described in Example 5 of the aforementioned Cromwell and'Merley patent. The sulfonic acid 30 obtained is rendered anhydrous and converted into a water-insoluble ester by reaction with ethylene oxide and then sulfated in the manner indicated in Example 1, preceding. I Example 11 Example 12 V The same procedure is followed as in Examples l-ll, inclusive, of the present instance, except that four to six moles of ethylene oxide are used instead of one to three.

Example 13 Propylene or butylene oxide is substituted for ethylene oxide in Examples 1-12, inclusive, of

- the present instance.

Example 14 The same procedure is followed as in Examples 1-13, inclusive, except that an amine of the kind exemplified by monoamylamine, cyclohexylamine, or benzylamine is used as a neutralizing agent.

It is to be noted that the last example illustrates a type in which the compounds obtained are water-insoluble. Such water-in-oil types are particularly adaptable for many purposes, and in fact, in many instances are just as desirable, or even more desirable, for demulsiflcation of certain crude oils than are the corresponding watersoluble types. In the sulfation step it has been previously pointed out that a solvent may be employed, particularly if the material employed is substantially solid at the sulfation temperature. A class of very' suitable solvents includes the chlorinated alkanes, such as chloroform, carbon tetrachloride, trichlorethylene, dichlorpentane, etc. Incidentally, in some instances, particularly where glycidol is used for oxyalkylation, one may obtain an ester in which more than one said sulfate radical is introduced.

Conventional demulsifying agents employed in the treatment of oil field emulsions are used as such, or after dilution with any suitable solvent. such as water; petroleum hydrocarbons, such as gasoline, kerosene, stove oil, a coal tar product. such as benzene, toluene, xylene, tar acid oil, cresol, anthracene oil, etc. Alcohols, particularly aliphatic alcohols, such as methyl alcohol, ethyl alcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc.

may be employed as diluents. Miscellaneous solvents. such as pine oil, carbon tetrachloride,

Similarly, the material or materials herein described, may be admixed with one or more of the solvents customarily used in connection with conventional demulsifying agents. Moreover, said-material or materials. may be used alone, or in admixture with other suitable well known classes of demulsifying agents.

It is well known that conventional demulsifying agents may be used in a-water-soluble form, or in an oil-soluble form, or in a form exhibiting ,both oil and water solubility. Sometimes they may be used in a form which exhibits relatively limitedoil solubility. However, since such reagents are sometimes used in a ratio of 1 to 10,000 or 1 to 20,000 or even 1 to 30,000, such an apparent insolubilityin oil and water is not significant, because said reagents undoubtedly have solubility within the concentration employed. This same fact is true in regard to the material or materials herein described. a

We desire to point out that the superiority of the reagent or demulsifying agent contemplated in our herein described process for breaking petroleum emulsions, is based upon its ability to treat certain emulsions more advantageously and at a somewhat lower cost than is possible with other available demulsifiers, or conventional mixtures thereof. It is believed that the particular demulsifying agent or treating agent herein described will find comparatively limited apnlica tion, so far as the majority of oil field emulsions are concerned; but we have found that such a demulsifying agent has commercial value, as it will economically break or resolve oil field emulsions in a number of cases which cannot be treated as easily or at so low a cost with the demulslfying agents heretofore available.

In practicing our process, a treating agent or demulsifying agent of the kind above described is brought into contact with or caused to act upon the emulsion to be treated, in any of the various ways, or my any oi the various apparatus now generally used to resolve or break petroleum one with a chemical reagent, the above procedure being used either alone or in combination with other demuisifyins procedure, such as the electrical dehydration process.

The demulsifier herein contemplated may be employed in connection with what is commonly known as down-the-hole procedure, i. e., bringing the demulsifier in contact with the fluids of the well at the bottom of the well, or at some point prior to their emergence. This particular type of application is decidedly feasible when the demulsifier is used in connection with acidification of calcareous oil-bearing strata, especially if It may be well to emphasize that the compounds of the kind herein contemplated may be manufactured by any suitable method; and it is .not intended to limit the compounds to any particular method of manufacture. When manufactured by the use of an alkylene oxide, it is our preference to use ethylene oxide, propylene oxide, or butylene oxide.

It is to be noted that the sulfato sulfonates and the sulfato sulfonic acids referred to in the claims are surface-active in the same sense that sulfonic acids themselves are surface-active. Furthermore, it is to be noted that some sulfonic acids might be of the polysulfonic acid type, i. e., as exemplified by disulfonic acids. There is no objection to the use of such raw materials as reactants, and it is obvious that such procedure presents a means by which one obtains an ester in which either one or both terminal hydroxyl radicals may be sulfated.

Once more attention is directed to the fact that in the hereto appended claims the reference to an acyl group is not to the acyl group derived from the carboxyl radical, but to the acyl group derived from the sulfonic acid radical. Furthermore, it is understood that it is immaterial what form the carboxyl radical takes, 1. e., whether it is present in the form of the free acid, in the form of the salt, or in the form of the ester. All this has been indicated previously.

Having thus described our invention, what we claim as new and desire to secure by Letters Patent is: y

1. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsisuspended in or dissolved in the acid employed 7 v, for acidification.

In the hereto appended claim, the word acylis used in reference to the radical R802; 1. e., one can conveniently consider the sulfonic acid RSOaH in terms of a formula indicating part of its structure, to wit: R.S0:. OH.

In the hereto appended claims the words polyhydridic alcohol" are used in the conventional sense to include not only materials of the type exemplified by ycerol and ethylene g col, but

also materials of the End in which the carbon 'fier comprising sulfato sulfonate derived from a polyhydric alcohol in which one hydroxy hydrogen atom has been replaced by the acyl radical of an alicyclic sulfonic acid derived from the group consisting of dipentene, the diamylenes, turpentine, alpha and beta pinenes, pine oil, abietic acid, methyl abietate, tallol, and dihydromethyl abietate; and another hydroxy hydrogen atom of said polyhydric alcohol has been replaced by the linkage:

jecting the emulsion to the action of a demulsifier comprising a water-soluble sulfato sulfonate derived from a polyhydric alcohol in which one hydroxy hydrogen atom has been replaced by the acyl radical of an alicyclic sulfonic acid derived from the group consisting of dipentene, the diamylenes, turpentine, alpha and beta pinenes, pine oil, abietic acid, methyl abietate, tallol and di-hydrcmethyl abietate; and another hydroxy hydrogen atom of said polyhydric alcohol has been replaced by the linkage:

is- V which in turn is united with a cation; said compound being further characterized by the fact thatthej selected sulfonic acid and selected polyhydric alcohol must be such that the hydroxyl ated ester derived by replacing one hydroxy hydrogen atom of the aforementioned polyhydic alcohol by the aforementioned acyl radical in water-insoluble. 3. A process for breaking petroleum emulsions -of the water-in-oil type, characterized by sub- 'jecting the emulsion to the action of a demulsifier comprising a water-soluble sulfato sulfonate derived from an aliphatic polyhydric alcohol in which one hydroxy hydrogen atom has been replaced by the acyl radical of an alicyclic sulfonic acid derived from the group consisting of dipentene, the diamylenes, turpentine, alpha and beta pinenes, pine oil, abietic. acid, methyl abietate, tallol, and dihydromethyl abietate; and another hydroxy hydrogen atom of said poly- I hydric alcohol has been replaced by the linkage:

of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifier comprising a neutral water-soluble sulfato I sulfonate derived from an aliphatic polyhydric alcohol in which one hydroxy hydrogen atom has been replaced by the acyl radical of an alicyclic sulfonic acid derived from the group consisting of dipentene, the diamylenes, turpentine, alpha and beta pinenes pine oil, abietic acid, methyl abietate,' tallol, and dihydromethyl abietate; and another hydroxy hydrogen atom of said polyhydric alcohol has been replaced by the linkage:

0 ii 0 ii which in turn is united with a cation; said compound being further characterized by the fact that the selected sulfonic acid and selected polyhydric alcohol must be such that the hydroxylated ester derived by replacing one hydroxy hydrogen atom of the aforementioned polyhydric alcohol by the aforementioned acyl radical is water-insoluble.

5. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a 'demulsifier comprising a neutral water-soluble sulfato sulfonate derived from an aliphatic polyhydric alcohol in which one hydroxy hydrogen atom has been replaced by the acyl radical of an alicyclic sulfonic acid derived from the group consisting of dipentene, the diamylenes, turpentine, alpha and beta pinenes, pine oil, abietic acid, methyl abietate, tallol, and dihydromethyl abietate; and another hydroxy hydrogen-atom of said polyhydric alcohol has been replaced by the linkage:

which in turn is united with acation; said compound being further characterized by the fact that'the selected sulfonic acid and selected polyhydric alcohol must be such that the hydroxylated ester derived by replacing one hydroxy hydrogen atom of the aforementioned polyhydric alcohol by, the aforementioned acyl radical is water-insoluble; said aliphatic polyhydric alcohol being characterized by the fact that the hydrocarbon radical present contains at least two car-' bon, atoms and not more than six carbon atoms.

6. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifier comprising a neutral water-soluble sulfato sulfonate derived from an aliphatic polyhydric alcohol in which one hydroxy hydrogen atom has been replaced by the acyl radical of an alicyclic sulfonic acid derived from the group consisting of dipentene, the diamylenes, turpentine, alpha i and beta pinenes, pine oil, abietic acid, methyl abietate, tallol, and dihydromethyl abietate; and another hydroxy hydrogen atom of said polyhydric alcohol has been replaced by the linkage:

which in turn is united with a cation; said compound being further characterized by the fact that the selected sulfonic acid and selected polyhydric alcohol must be such that the hydroxylated ester derived by replacing one hydroxy hydrogen atom of the aforementioned polyhydric alcohol by the aforementioned acyl radical is water-insoluble; said aliphatic polyhydric alcohol ibeing characterized by the fact that the hydrocarbon radicalpresent contains at least two carbon atoms and not more than six carbon atoms; and said sulfonic acid being free from any added aromatic radical.

7. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulsifier comprising a water-soluble sulfato sulfonate acid; and another hydroxy hydrogen atom of said mlyhydric alcohol has been replaced by the linkage:

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which in turn is united with a cation; said compound being further characterized by the fact that-the selected sulfonic acid and selected polyhydric alcohol must be such that the hydroxylated ester derived by replacing one hydroxy hydrogen atom of the aforementioned polyhydric alcohol by the aforementioned acyl radical is water-insoluble; said aliphatic po yhydric alcohol being characterized by the fact that the hydrocarbon radical present contains at least two carbon atoms and not more than six carbon atoms; and said sulfonic acid being free from any added aromatic radical. V

8. A process forbreaking petroleum emulsions of the water-in-oil type, characterized by sub-' jecting the emulsion to the action of a demulsifier comprising a water-soluble sulfato sulfonate derived from an aliphatic polyhydric alcohol in which one hydroxy hydrogen atom has been replaced by the acyl radical of a pinene sulfonic acid: and another hydroxy hydrogen atom of said polyhydric alcohol has been replaced by the linkage:

which in turn is united with a cation: said compound being further characterized by the fact. 10

that the selected sulfonic acid and selected polyhydric alcohol must be such that the hydroxylated ester derived by replacing one hydroxy hydrogen atom of the aforementioned polyhydric alcohol by the aforementioned acyl radical is water-insoluble; said aliphatic polyhydric alcohol being characterized by the fact that the hydrocarbon radical present contains at least two carbon atoms and not more than six carbon atoms;

and said sulfonic acid being free from any added aromatic radical.

9. A process for breaking petroleum emulsions of the water-in-oil type, characterized by subjecting the emulsion to the action of a demulslfier comprising a water-soluble sulfato sulfonate derived from an aliphatic polyhydric alcohol in which one hydroxy hydrogen atom has been replaced by the acyl radical of a pine oil sulfonic acid; and another hydroxy hydrogen atom of said polyhydric alcohol has been replaced by the linkage:

which in turn is united with a cation; said compound being further characterized by the fact that the selected sulfonic acid and selected polyhydric alcohol must be such that the hydroxylated ester derived by replacing one hydroxy hydrogen atom of the aforementioned polyhydric alcohol by the aforementioned acyl radical is water-insoluble; said aliphatic polyhydric alcohol 

